RESUMO
The treatment of primary or secondary alkyl iodides with sBu2 Mg in toluene (25-40 °C, 2-4â h) provided dialkylmagnesiums that underwent various reactions with aldehydes, ketones, acid chlorides or allylic bromides. 3-Substituted secondary cyclohexyl iodides led to all-cis-3-cyclohexylmagnesium reagents under these exchange conditions in a highly stereoconvergent manner. Enantiomerically enriched 3-silyloxy-substituted secondary alkyl iodides gave after an exchange reaction with sBu2 Mg stereodefined dialkylmagnesiums that after quenching with various electrophiles furnished various 1,3-stereodefined products including homo-aldol products (99 % dr and 98 % ee). Mechanistic studies confirmed a radical pathway for these new iodine/magnesium-exchange reactions.
RESUMO
We report a type of highly efficient double hydrogen atom transfer (DHAT) reaction. The reactivities of 3-aminopropanol and 2-aminoethanol towards Criegee intermediates (syn- and anti-CH3 CHOO) were found to be much higher than those of n-propanol and propylamine. Quantum chemistry calculation has confirmed that the main mechanism of these very rapid reactions is DHAT, in which the nucleophilic attack of the NH2 group is catalyzed by the OH group which acts as a bridge of HAT. Typical gas-phase DHAT reactions are termolecular reactions involving two hydrogen bonding molecules; these reactions are typically slow due to the substantial entropy reduction of bringing three molecules together. Putting the reactive and catalytic groups in one molecule circumvents the problem of entropy reduction and allows us to observe the DHAT reactions even at low reactant concentrations. This idea can be applied to improve theoretical predictions for atmospherically relevant DHAT reactions.
RESUMO
The photoinduced tautomerization reactions via hydrogen atom transfer in the excited electronic state (ESHT) have been computationally investigated in 2,7-diazaindole (27DAI) - (H2O)1-3 and 27DAI - (NH3)1-3 isolated clusters to understand the role of various solvent wires. Two competing ESHT reaction pathways originating from the N(1)-H group to the neighbouring N(7) (R(1H-Sn-7H)) and N(2) (R(1H-Sn-2H)) atoms were rigorously examined for each system. Both one- and two-dimensional potential energy surfaces have been calculated in the excited state to investigate the pathways. The R(1H-Sn-7H) was found to be the dominant route with reaction barriers ranging from 26-40 kJmol-1 for water clusters, and 14-26 kJmol-1 for ammonia clusters. The barrier heights for ammonia clusters were found to be nearly half of the that observed for the water systems. The lengthening of the solvent chain up to two molecules resulted in a drastic decrease in the barrier heights for R(1H-Sn-7H). The barriers of the competing reaction channel R(1H-Sn-2H) were found to be significantly higher (31-127 kJmol-1) but were observed to be decreasing with the lengthening of the solvent wire as in the R(1H-Sn-7H) pathway. In both the reactions, the angle strain present in the transition state structures was dependent upon the solvent chain's length and was most likely the governing factor for the barrier heights in each solvent cluster. The results have also affirmed that the ammonia molecule is a better candidate for hydrogen transfer than water because of its higher gas-phase basicity. The results delineated from this investigation can pave the way to unravel the excited-state hydrogen atom transfer pathways in novel N-H bearing molecules.